Reactive monoazo dyes



United States Patent:

3,523,115 REACTIVE MONOAZO DYES Philippe Grandjean, Basel, Switzerland, assignor t0 Sandoz Ltd. (alsoknown as Sandoz A.G.), Basel, Switzerland No Drawing. Filed Mar. 13, 1967, Ser. No. 622,454 Claims priority, application S/vgizerland, Mar. 28, 1966,

7 Int. Cl. C09b 29/30; D06p 1/02 US. Cl. 260-153 6 Claims ABSTRACT OF THE DISCLOSURE Reactive dyes of the formula NH-X wherein A is a lower alkylene or a lower hydroxyalkylene radical, Z is hydrogen, chlorine, bromine, lower alkyl or --COOH,

and

X is a reactive radical.

DESCRIPTION This invention relates to valuable reactive dyes of the formula lZ OH H0 8 NH-X wherein A stands for an alkylene radical which has 2 or 3 carbon atoms and may bear a hydroxyl group,

X for a radical containing at least one substituent cleavable as an anion and/or a multiple linkage capable of addition, and

Z for hydrogen, chlorine, bromine, lower alkyl or COOH.

where Y stands for hydrogen or SO H, followed by treatment with a sulfating agent when Y stands for hydrogen, the aforesaid reaction and coupling being carried out in either order.

ice

A second mode of operation of this process consists in coupling 1 mole of the diazo compound of an amine of Formula II with 1 mole of 2-acylamino-S-hydroxynaphthalene-7-sulfonic acid, splitting off the acyl group and reacting the amino group with at least 1 mole of an acylating agent containing at least one substituent cleavable as an anion and/ or a multiple linkage capable of addition or of a dihalogenoor trihalogeno-1,3,5,-triazine or of a trihalogenoor tetrahologenopyrirnidine, and, when Y stands for hydrogen, treating the dye with a sulfating agent at any desired stage in the replacement of the acyl group by the radical X.

Examples of suitable groups YO-A in which Y stands for hydrogen are a H; OH

In the first mode of operation of the process the procedure may be, for example, as follows:

(a) the coupling component is reacted with the reactive component, then the coupling reaction is effected and, when Y stands for hydrogen, the resulting dye sulfated; or

(b) the coupling reaction is carried out, then the reactive radical X is introduced and, when Y stands for hydro gen, the dye sulfated either before or after the introduction of the reactive radical X.

The second mode of operation of the process also admits of several alternative procedures. For example, when Y stands for hydrogen, it may take these forms:

i (d) the coupling reaction is performed, the acyl group split off and the amino group reacted with the reactive component.

The radical X bears at least one substituent cleavable as an anion, preferably a chlorine or bromine atom or a sulfato group OSO H, and/or a C-C multiple linkage capable of addition, preferably an ethylene group which is bound to a carbonyl or sulfonyl group and may be substituted. This radical may be, for example, a reactive aliphatic or heterocyclic acyl radical derived from one of the following acids: chloroacetic, bromoacetic, ,B- chloropropionic, 3 bromopropionic, acrylic, on chloroacrylic, u-bromoacrylic, 0a,;8-dl0hl01'0- or pfi-dichloroacrylic, u,,8-dibromoor 'fi, 3-dibromo-acrylic, y-chlorocrotonic or 'y-bromocrotonic, vinylsulfonic, ,B-chlorethaneor fi-bromethanesulfonic, B-sulfatopropionic, /3-sulfatoethane-sulfonic, 2,4-dichloroorv 2,4-dibromo-pyrimidine- S-carboxylic, 2,4-dichloroor 2,4-dibromo-6-methylor 6-chlorornethylor -6-dichloromethylpyrimidine 5 carboxylic, 2,3-dichloroor 2,3 dibrornoquinoxalinee6-carboxylic or 6-sulfonic or 6-carbamic acids. Alternatively,

3 this radical may be a 4,6-dichloroor 4,6-dibromo-l,3,5- triazinyl-Z radical or a radical of formula where Hal represents chlorine or bromine, and v the radical, which may be further substituted, of a primary or secondary aliphatic, alicyclic, aromatic or heterocyclic amine, of .an aliphatic or aromatic hydroxyl compound, or in particular the radical of aniline, its alkyl or sulfonic acid or carboxylic acid derivatives, the radical of lower monoalkyl or dialkyl amines, or the radical of ammonia;

or it may be a dihalogenoor trihalogeno-pyrimidyl radical or a 2,4-dihalogenopyrimidyl-S-methylene radical. The three last-named radicals are derived from pyrimidine components, for example from 2,4,6-tn'chloroor 2,4,6-tribromo-pyrimidine or their derivatives which are substituted in the 5-position, for example by methyl, carboxy, carboxymethyl, chloromethyl or bromomethyl,

or from 2,4,6-trich1oro-5-bromopyrimidine,

2,4,5,6-tetrachloroor 2,4,5,6-tetrabromo-pyrimidine,

2,4-dichloro-S-chloromethylpyrimidine,

2,4-dibromo-5-bromomethylpyrimidine,

2,4-dichloro-5-chloromethyl-6-methylpyrimidine or 2,4-dibromo-5-brornomethyl-6-methylpyrimidine.

The reactive radical X can be 1. lower aliphatic acyl substituted by one or two halogen atoms or a sulfato group cleavable as anion(s), e.g., (a) monohaloflower) alkanoyl, (b) dihalo(lower)alkanoyl, (c) monohalo (lower) alkylsulfonyl, (d) sulfatoflower) alkylsulfonyl and (e) sulfato(lower)alkanoyl, and/or containing a 0-0 double bond, e.g. (f) (lower)alkenoyl, (g) monohalo (lower)alkenoyl, (h) dihalo(lower)alkenoyl and (1) (lower) alkenylsulfonyl; l1. dihalopyrimidyl carbonyl, e.g.,

(a) 2,4-dihalopyrimidyl-S-carbonyl,

(b) 2,4-dihalo-6-methylpyrimidyl-S-carbonyl,

(c) 2,4-dihalo-6-halomethylpyrimidy1-5-carbony1 and (d) 2,4-dihalo-6-dihalomethylpyrimidyl-S-carbonyl;

III. dihaloquinoxalylcarbonyl, e.g.,

2,3-dihaloquinoxalyl-6-carbony1;

IV. dihaloquinoxalyl-sulfonyl, e.g.

2,3-dihaloquinoxalyl-6-sulfonyl;

V. dihaloquinoxalylaminocarbonyl, e.g.

2,3-dihaloquinoxalyl-6-aminocarbonyl;

VI. monohaloor dihalo-l,3,5-triazinyl, e.g.

(a) 4,6-dihalo-1,3,5-triazinyl-2,

(b) 4-ha1o-6-(lower)alkoxy-l,3,5-triazinyl-2,

(c) 4-halo-6-phenoxy-1,3,5-triazinyl-2,

(d) 4-halo-6-amino-1,3,5-triazinyl-2,

(e) 4-halo-6-(lower)alkylamino-1,3,5-triazinyl-2,

(f) 4-halo-6-di(lower)alky1amino-1,3,5-|riazinyl-2,

(g) 4-halo-6-hydroxy(1ower)alkylamino-l,3,5-triazinyl-2,

(h) 4-halo-6-di[hydroxy(lower)alkyl]amino-1,3,5-triazinyl-Z,

(i) 4-halo-6-N lower) alkyl-N-hydroxy (lower) alkylamino-1,3,5-triaziny1-2,

(j) 4-halo-6- (lower) alkoxyflower) alkylamino-l ,3,5-

triazinyl-2,

(k) 4-halo-6-carboxy(1ower)alky1amino-l,3,5-triazinyl-2,

(l) 4-halo-6-N-(lower)alkyl-N-carboxy(lower) alkylamino-1,3,5-triazinyl-2,

(m) 4-halo-6-su1fo (lower)alkylamino-1,3,5-triazinyl-2,

(n) 4-ha1o-6-N- (lower) alkyl-N-sulfo (lower) alkylamino- 1,3,5-triazinyl-2,

(o) 4-halo-6-phenylamino-1,3,5-triaZinyl-2,

(p) 4-halo-6-methylphenylamino-1,3,5-triazinyl-2,

(q) 4-halo-6-N-(lower)alkyl-N-phenylamino-1,3,S-triazinyl-Z,

(r) 4-halo-6-N-hydroxy(lower)alkyl-N-phenylamino- 1,3,5-triazinyl-2, (s) 4-halo-6-carboxyphenylamino-l,3,5-triazinyl-2, (t) 4-halo-6-sulfophenylamino-l,3,5-triazinyl-2, (u) 4-halo-6-dicarboxyphenylamino-1,3,S-triazinyl-Z, (v) 4-halo-6-carboxysulfophenylamino-1,3,5-triazinyl-2, (w) 4-halo-6-disulfophenylamino-1,3,5-triazinyl-2 (x) 4-halo-6-sulfonaphthylamino-1,3,5-triazinyl-2 and (y) 4-halo-6-disulfonaphthylamino-1,3,5-triazinyl-2;

or VII. dior trihalopyrimidyl, e.g.,

(a) 2,4-dihalo-6-methylpyrimidyl-S-methylene, (b) 2,4-dihalopyrimidyl-S-methylene,

(c) dihalopyrimidyl,

(d) trihalopyrimidyl,

(e) 5-(lower) alkyl-dihalopyrimidyl,

(f) 5- (lower) alkoxycarbonyl-dihalopyrimidyl, (g) S-carboxy-dihalopyrimidyl,

(h) 5-halomethyl-dihalopyrimidyl and *(i) 5-carboxymethyl-dihalopyrirnidyl;

halo in each instant being either chloro or bromo.

Normally, the introduction of the reactive aliphatic acyl radicals can be elfected most easily by using the corre sponding acid halides or in some cases the acid anhydrides. It is preferably to work at low temperatures, for example at 0 to 20 C., in the presence of acid-binding agents, such as sodium carbonate, sodium hydroxide, calcium hydroxide or sodium acetate, and in a weakly acid, neutral or weakly alkaline medium, for example in the pH-range of 4 to 9. For the purpose of acylation the carboxylic acid chlorides can be employed as they are or in solution in two to five times their amount of benzene, chlorobenzene, methylbenzene, dimethylbenzene or acetone, and they are added dropwise to the aqueous, Well bufiered solution of the compound bearing the amino group at a temperature of, e.g., 2-5 C. Acylation with the anhydrides can be carried out in the same manner.

For the introduction of the reactive heterocyclic acyl radicals: 2,-4 dichloroor 2,4-dibrom0-pyrimidyl-5-carbonyl or the 2,3-dichloroor 2,3-dibromo-quinoxa1yl-6- carbonyl or -6-sulfonyl radicals, it is convenient to use the acid halides or preferably the acid chlorides. The acid halides can be employed as they are or in solution in an organic solvent, such as dioxan, acetone, benzene, toluene or chlorobenzene, and the reaction can be conducted in the temperature range of 0 to about 60 C., preferably at 0-25 C. for the 2,4-dichloroor 2,4-dibromo-pyrimidine-S-carboxylic acid halides or 20-55 C. for the 2,3- dichloroor 2,3 dibromo-quinoxaline-6-carboxylic acid or -6-suifonic acid halides, and at a pH value of 3 to 8 or preferably, 4 to 7.

The reaction with the 2,3-dichloroor 2,3-dibromoquinoxaline-G-isocyanates can be carried out in an analogous manner.

The introduction of a dihalogeno-cyanuric radical is effected most expediently in aqueous medium at about 0 (3., e.g. at 0 to 10 (3., and at a weakly acid reaction, e.g., at a pH value of 3 to 6. The cyanuric halide can be employed in solid form or in solution in an organic solvent, such as acetone. For the primary condensation products of a cyanuric halide it is best to choose a temperature of 30 to 60 C. and a pH value of 4 to 7, whereas for the trihalogenoand tetrahalogeno-pyrimidines the temperature may range from 20 to C. It is advisable to work with a reaction vessel fitted with a reflux condenser in view of the volatility in water vapour of certain halogenopyrimidines. By employing approximately equimolar amounts, the reaction is conducted so that only one halogen atom reacts with one exchangeable hydrogen atom of the amino group. The reaction can be carried out in a weakly alkaline, neutral or Weakly acid medium, though it is preferably to remain within the pH range of 9 to 3. To neutralise the equivalent of hydrogen halide which is formed, an acid-binding agent, such as sodium acetate, is added to the solution at the beginning of the reaction or, alternatively, small portions of sodium or potassium carbonate or bicarbonate in solid pulverised form or in concentrated aqueous solution are added during the course of the reaction. Aqueous solutions of sodium or potassium hydroxide are also suitable as neutralising agents.

The addition of small amounts of a wetting or emulsifying agent to the reaction mixture can accelerate the rate of reaction.

The amine of Formula II is best diazotised by the direct method at temperatures of to 15 C., or preferably at -10 C., and coupled at 0 to about 30 C., or preferably 520 C., at a pH value of about 5.5 to 9, or preferably 6-7, When the coupling component bears a reactive radical X or at pH 7-8 when the coupling component is Z-amino-5-hydroxynaphthalene-7-sulfonic acid or one of its acyl derivatives, such as acetyl, propionyl, ethoxycarbonyl or methoxycarbonyl. The alkali required for neutralisation, e.g., sodium bicarbonate, can be added before the coupling reaction in one amount or in small portions during the coupling reaction.

If a 2-acylamino-S-hydroxynaphthalene-7-sulfonic acid is used as coupling component, its acyl group must be split otf after coupling. Cleavage of this group can be accomplished in mineral acid medium, e.g., in 2 to 10% hydrochloric or sulfuric acid, at 70 to 100 C., or in alkaline modium, e.g., 2 to 10% or preferably 2 to 5% sodium hydroxide or potassium hydroxide solution, at 80 C. to the boiling point of the solution or preferably at 90-95 C. Cleavage of the acyl group in the sulfated dye is carried out at 90100 C. in alkaline medium, e.g. 2-5% sodium or potassium hydroxide solution.

Examples of suitable sulfating agents are sulfuric acid of 93-100% strength, oleum, preferably of 0-25% strength, or chlorosulfonic acid. Sulfation is carried out at 0 to 80 C., e.g., at 10 to 80 C. or preferably to 50 C. when concentrated sulfuric acid is used, or at 0 to 40 C. when oleum or chlorosulfonic acid is used. After coupling or sulfation, or after the introduction of the X group, the monoazo dyes are precipitated from the aqueous solution by the addition of salt, filtered off, Washed if necessary and dried.

These dyes are suitable for dyeing leather and for dyeing, padding or printing wool, silk, synthetic polyamide fibers and fibers of natural or regenerated cellulose, for example cotton, linen, hemp, viscose rayon and cuprammonium rayon, and for blends and/ or other materials of these fibers. They are particularly suitable for the exhaustion dyeing of natural or regenerated cellulosic fibers.

During or after dyeing, padding or printing the goods are treated with acid-binding agents, e.g., in the cold, i.e., at 20 to 40 C., when the reactive group Y is a 4,6- dihalogeno-1,3,5-triazinyl-2-group, or preferably at elevated temperature, e.g., at 80 to 100 C. or higher, when the reactive group X is a monohalogeno-1,3,5-triazinyl-2- or polyhalogenopyrimidyl group. The normal wetting, levelling and thickening agents and other textile and leather auxiliary products can be used for dyeing, padding and printing. For wool, silk and synthetic polyamide fibers it is best to use acid-binding agents which give a pH value of 5 to 8, for example acetate or phosphate buffers, hexamethylene tetramine, or sodium carbonate or bicarbonate when acetic acid is used for dyeing. Suitable acidbinding agents for natural and regenerated cellulosic fibers are sodium carbonate and bicarbonate, sodium metasilicate, sodium hydroxide, trisodium phosphate and the analogous potassium compounds.

The dyeings and prints produced on cellulosic fibers with these dyes have very good fastness to wet tests, such as water, washing at 95 C., perspiration, soda boiling and alkaline hydrolytic influences, especially at the boil to gether with good fastness to rubbing, stoving, chlorinated swimming pool water and dry cleaning.

The new dyes reserve acetate, triacetate, polyvinyl chloride or acetate, polyacrylonitrile, linear aromatic polyester and polyalkylene fibers. In comparison with the next comparable reactive monoazo dyes, which in place of the radical HO SOA-O- hear an alkoxy radical, such as CH O or C H --O- plus a sulfonic acid group bound to the benzene nucleus (see French Pat. 1,221,621, Example 26, and French patent of addition 75,771, Example 26), the dyes of the present invention have better solubility in water and a higher degree of fixation on cellulosic fibers.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 47.8 parts of 2-amino-5-hydroxynaphthalene 7 sulfonic acid are dissolved in 800 parts of water at a weakly acid reaction with the addition of 10% sodium hydroxide solution. 43.6 parts of 2,4,5,6-tetrachloropyrimidine are added and the reaction mixture is stirred for a few hours at 5060, its pH being maintained at 4.0 to 4.5 during this time by dropwise addition of dilute sodium carbonate solution. On completion of the reaction the resulting sodium 2 trichloropyrimidylamino 5 hydroxynaphthalene-7-sulfonate is completely precipitated by the addition of sodium chloride and is suctioned off, washed with dilute sodium chloride solution and dried.

In the meantime 233 parts of the acidic sulfuric acid ester of l-amino-4-(2"-hydroxyethoxy)-benzene are dissolved in 400 parts of water at room temperature with the addition of 4 parts of sodium hydroxide. To this solution are added 6.9 parts of sodium nitrite. The solution is added dropwise to a mixture of 25 parts of 30% hydrochloric acid and 50 parts of ice and the suspension thus formed is stirred further at 5l0 until diazotisation is complete.

42.3 parts of sodium 2-trichloropyrimidylamino-5-hydroxynaphthalene-7-sulfonate are stirred into 60-0 parts of water at room temperature. The mixture is raised to 6070 and held at this temperature until everything goes into solution. The resulting solution is cooled to 20 and in the course of 30 minutes the diazo suspension is run into it in a fine jet. At the same time 20% sodium carbonate solution is dropped in to maintain the pH-value constant at 6.5. On completion of coupling, the reaction mixture is raised to 70 and the monoazo dye formed is precipitated by the addition of sodium chloride, filtered off and dried. It is a red powder which dissolves in water to give scarlet solutions; it dyes cotton and regenerated cellulosic fibers in scarlet shades. The dye dis solves in water at 30 in amounts greater than 50 grams per liter and it has a high fixation yield on cellulosic fibers.

Application example 2 parts of the dye described in Example 1 are dissolved in 4000 parts of softened water at 40. parts of a mercerised and previously wetted out cotton fabric are entered into this bath, on which parts of calcined sodium sulfate and 30 parts of calcined sodium carbonate are added. The bath is then raised to 100 in 30 minutes, with a further addition of 110 parts of calcined sodium sulfate after 10 minutes and 100 parts after 20 minutes. On reaching boiling temperature, a final 50 parts of calcined sodium carbonate are added and the bath is held at the boil for 1 hour. The dyed fabric is then removed, rinsed with water and dried. The scarlet dyeing obtained is fast to light and wet treatments.

The degree of fixation of the new dye is apprecially greater than that of the analogous dye containing an ethoxy group in para-position to the azo group and a sulfonic acid group in orthoposition to the azo group.

EXAMPLE 2 The diazo suspension prepared in accordance with the particulars of Example 1 is combined at 5-l0 with a neutral solution of 23.9 parts of 2-amino-5-hydroxynaphthalene-7-s'ulfonic acid in 500 parts of water and 13.5 parts of 30% sodium hydroxide solution. The pH value is maintained at 7 to 8 by the gradual addition of sodium bicarbonate. The aminomonoazo dye formed is precipitated with sodium chloride and filtered off.

The filter cake is entered into 1000 parts of water to form a neutral solution which is run in the course of 2 hours into an ice-cold suspension of 20 parts of cyanuric chloride in 100 parts of water. The pH value is kept at 4 to 5 by adding 20% sodium carbonate solution. The suspension is stirred at until no further aminomonoazo dye is present, on which it is raised to 40 and a neutral solution of 17.3 parts of l-aminobenzene-3-sultonic acid added to it. Stirring is continued for 4 hours, during which time the pH value is kept at about 7 by adding 20% sodium carbonate solution. On completion of this second condensation reaction the dye is salted out, filtered oil, and dried. It is obtained as a dark powder which dissolves in water with a scarlet colour and dyes cotton and regenerated cellulosic fibers in scarlet shades.

EXAMPLE 3 The aminomonoazo dye formed as described in Example 2 is dissolved in 1000 parts of water, and this neutral solution is gradually added over 2 hours to a solution of 34.3 parts of sodium 4-(4,6'-dichloro-1,3,5'- triazinyl-2'amino)-benzene-l sulfonate in 350 parts of water at 35-40". The combined solution is stirred for a few hours at 3540, with the simultaneous addition of 20% sodium carbonate solution to maintain the pH- value at 6-7. When the reaction has run its course the dye is salted out, filtered oil and dried. A dark powder is obtained which dissolves in water to give scarlet solutions; this dye gives dyeings of scarlet shade on cotton and regenerated cellulosic fibers.

EXAMPLE 4 15.3 parts of l-amino-4-(2-hydroxyethoxy)-benzene are dissolved at room temperature in 300 parts of water and 20 parts of 30% hydrochloric acid, and diazotised at 5-10 by the addition of 6.9 parts of sodium nitrite. The resulting diazo solution is allowed to run slowly into a neutral solution of 30.3 parts of sodium 2-acetylamino-5- hydroxynaphthalene-7-sulfonate in 500 parts of water at 5-10, the pH value being maintained at 7-7.5 by the simultaneous addition of sodium carbonate solution. The dye thus formed is salted out and filtered oil with suction. In the paste form as thus obtained it is dissolved in 600 parts of 2% sodium hydroxide solution and stirred for 2 hours at 95, after which time it is completely deacetylated. The hot solution is filtered clear and adjusted to the pH-value of 7-8, on which the aminoazo dye is salted out, suctioned ofi and washed with sodium chloride solution.

The filter cake is dissolved in 1000 parts of water at 70 and 21.8 parts of 2,4,5,6-tetrachloropyrimidine are added thereto at 70-80 over a period of 2 hours. The pH value is kept at 6 to 7 by adding 20% sodium carbonate solution. When no further aminomonoazo dye is indicated, the newly formed tricholoropyrimidylamino dye is salted out with sodium sulfate, suctioned ofi and dried. It is gradually added over 1 hour at 5-l0 to 32 parts of 100% sulfuric acid and 32 parts of 25% oleum, and when the addition is complete, the temperature is increased to 20 and the solution stirred for 2 hours at this temperature. It is then discharged on to ice in such a manner that the temperature remains at 05. The precipitated dye is filtered off and converted into the sodium salt by dissolving in dilute sodium carbonate solution and precipitation with sodium chloride. The salt is then filtered oil and dried. It is obtained as a red powder which dissolves in water with a scarlet colour and gives dyeings of scarlets shade on cotton and regenerated cellulosic fibers.

8 EXAMPLE 5 The diazo suspension prepared in accordance with the procedure of Example 1 is run slowly at 510 into a neutral solution of 30.3 parts of sodium Z-acetylarnino- 5-hydroxynaphthalene-7-sulfonate in 500 parts of water. Sodium carbonate solution is added at the same time to maintain the pH-value at 7-7.5. The dye formed is salted out and suctioned off. In the paste form as obtained it is stirred in 600 parts of 2% sodium hydroxide solution for 2 hours at after which time deacetylation is complete. The hot solution is filtered clear and the aminoazo dye salted out, suctioned oh" and washed with sodium chloride solution.

The filter cake is dissolved in 1000 parts of water at 40 and the solution cooled to 0-5 to receive a solution of 16 parts of fl-chloropropionic acid chloride in 25 parts of benzene, which is added over 2 hours at the latter temperature. The pH-value is held at 6 to 7 by adding 20% sodium carbonate solution. When no further aminomonoazo dye is indicated, the solution is raised to 20 and the resulting fl-chloropropylamino dye salted out with sodium chloride, suctioned off and dried. It is a red powder which dissolves in water to give scarlet solutions; it gives dyeings of scarlet shade on cotton and regenerated cellulosic fibers.

EXAMPLE 6 The procedure of Example 5 is followed with the difference that a solution of 23.5 parts of 2,4-dichloropyrimidine-S-carboxylic acid chloride in parts of ace tone is used in place of the ,B-chloropropionic acid chloride solution. The dye formed is dried at 40" and is obtained as a red powder which dissolves in water with a scarlet colour and dyes cellulosic fibers in scarlet shades at temperatures as low as 20-40".

EXAMPLE 7 The moist filter cake of the aminoazo dye produced in accordance with the particulars of Example 5 is dissolved in 1000 parts of water at 40. To this solution 27 parts of finely pulverised 2,3-dichloroquinoxaline-tS-carboxylic acid chloride are added in small portions, and stirring is continued at 40-45 until no further free amino group is indicated. During the reaction time dropwise addition of 20% sodium carbonate solution serves to keep the pH-value constant at 5-6. The dye is isolated in the way described in Example 5. It dissolves in water with a scarlet colour, and its dyeings on cellulosic fibers are of scarlet shade and have high fastness to light and wet treatments.

EXAMPLE 8 The 2,3-dichloroquinoxaline-6-carboxylie acid chloride used in Example '7 is replaced by the equivalent amount of 2,3-dichloroquinoxaline-6-sulfonic acid chloride or 2,3- dichloroquinoxaline-fi-isocyanate. For the chloride a reaction temperature of 50-55" is preferable, while for the isocyanate 40-45" is the optimum; with the latter no addition of acid-binding agent is necessary. The dyes thus obtained are very similar to the dye of Example 7.

EXAMPLE 9 The diazo suspension prepared as detailed in Example 4 is combined at 5l0 with a neutral solution of 23.9 parts of 2-amino S-hydroxynaphthalene-7-sulfonic acid in 500 parts of water and 13.5 parts of 30% sodium hydroxide solution. The pH-value is maintained at 7 to 8 by the gradual addition of sodium bicarbonate. The aminomonoazo dye formed is precipitated with sodium sulfate, suctioned off and dried. It is entered with stirring into 100 parts of 100% sulfuric acid over a period of 30 minutes at 15-20". Stirring is continued for 2 hours at 30, after which the solution is cooled to 0-5 and run on to ice. The precipitated dye is filtered off and after being washed with water the filter cake is stirred into 500 parts of water to form a suspension, the pH-value of which is adjusted to 6-7 with 30% sodium hydroxide solution. The suspension is then held at 70-80 until everything is dissolved, on which 18.4 parts of 2,4,6-trichloropyrimidine are added, together with sufficient 20% sodium carbonate solution to keep the pH-value at 6-7. When the starting aminomonoazo dye is no longer indicated, the resulting dichloropyrimidylamino dye is salted out with sodium chloride, filtered olf and dried. It is obtained as a red powder which dissolves in Water to give scarlet solutions and dyes cotton and regenerated cellulosic fibers in scarlet shades.

EXAMPLE 10 The acetylamino dye obtained according to the procedure of Example 4 is produced as in that example, isolated and dried. It is added over 30 minutes to 50 parts of 100% sulfuric acid and 11.7 parts of chlorosulfonic acid at -5 following which the temperature is increased slowly to room temperature and the resulting solution run on to ice. The precipitated dye is filtered ofi and washed with water. The dye paste is entered into 800 parts of 3% sodium hydroxide solution and stirred for 2 hours at 95, after which time deacetylation is complete. The hot solution is filtered clear and adjusted to the pH-value of 7-8 with hydrochloric acid, after which the aminoazo dye is salted out, suctioned off and washed with sodium chloride solution. The filter cake is dissolved in 1000 parts of water at room temperature, and over a period of 1 hour this solution is run with stirring into an ice-cold aqueous suspension of 18.4 parts of cyanuric chloride, with simultaneous dropwise addition of dilute sodium hydroxide solution to maintain the pH-value at 5-6. On completion of the reaction, the dichlorotriazinyl dye formed is salted cotton or regenerated cellulosic fibers by the method described below, it gives scarlet dyeings.

Application examples 2 parts of the dye of Example 10 are dissolved in 3000 parts of softened water at Into this bath 100 parts of a previously wetted out cotton or viscose rayon staple fabric are entered, and over the next 30 minutes the bath is raised to with the gradual addition of parts of calcined sodium sulfate. Subsequently 6 parts of sodium hydrogen carbonate are added and the bath held at 60 for a further 30 minutes. Then 6 parts of calcined sodium carbonate are added in portions over 10 minutes and the bath is maintained at the same temperature for a further 15 minutes. The dyed fabric is then removed, rinsed with hot Water, soaped with a boiling 0.3% solution of a nonionic detergent, rinsed again and dried. A scarlet dyeing which is fast to light and wet tests is obtained.

EXAMPLE 11 The solution of the dichlorotriazinyl dye obtained as described in Example 10 is added to 20 parts of a 25% aqueous ammonia solution and stirred for 2 hours at 40. On completion the monochlorotriazinyl dye formed is salted out, filtered off and dried. It dyes cotton and regenerated cellulosic fibers by the method described in Example 1 in scarlet shades.

The following table contains details of further dyes which can be produced in accordance with the particulars given in Examples 1 to 11;' they are distinguished in columns (I) to (V) of the table, respectively, by the alkylene radical A, the substituent Z, the reactive component on which the radical X is based, the mode of production according to one of the Examples 1 to 11, and the out, filtered off and vacuum dried at 30-40. Applied to 35 shade of the dyeings on cellulosic or polyamide fibers.

TAB LE Substit- Example Radical A neat Z Reactive Component P c d as s d Number (I) in Example (IV) v OH OH H 2, 4, 6-tnch1oropyrimidine- 1 Scarlet --CH2CH2 H 2, 4, 6-tribromopyrimidine 1 D -C H -C H2 H 2, 4, 5, fi-tetrabromopyrimidine- 1 D 0 Hz-C H2 H 2, 4, 6-trichloro-5-methylpyrimidine 1 D 0 Hz-C Hz H 2, 4, 6-trichloro-5-bromopyridine 1 D O Hg-C H H 2, 4, 6-tri0hloro-5-chloromethylpyrimidine. 1 Do. 0 Hz-O H2- H 2, 4, 6-trichl0ro 5-carb oxypyrimidine 1 D --0 11 -0 E;- H 2, 4, 6-tricl1loro-5-carb oxymethylpyn'midine 1 Do CH2CHZCHZ H 2, 4, 5, G-tetrachloropyrimidine 4 D OH -CH- H 2,4,5,dtetrachloropyrimidine 4 D -CH2CH2 Cl 4 1) 2 2- 4 Do. 2 2- s 4 Do. CHzCH2- C2H5 4 D0, GH2CH2 COOH -d0 4 D0, C H2-C H2- H 2, 4-dichloro 5chloromethyl-6-methylpyrimidine 1 Do. 0 HzC HzC H2- H 2, 4, 6-trichloro-5-bromopyrimidine 1 D C He-C Hz- H chloroacetic acid chloride 5 1) -C H -C H H a-chloroacrylic acid chloride 5 D 0 H Hr- H cyanuric chloride, than fl-hydroxyethylamine a 2 D0. 0 H -C H;- H cyanuric chloride, then methylamine 2 D 0. -O Hz-O H;- H 2, 4dichlol'o-6-(2-carboxyphenylamino) -1, 3, 5-triazine 3 Do. 0 Hg-C H H bromoacetic acid bromide 5 D CH -CH H acrylic acid chloride 5 D C Hg-C H2- H 2, 4-dichloro-6-(2-sulfoethylamino)-1, 3, 5-triazine 3 Do. OH;O H;- H cyanuric bromide 10 D n -C H2G Hz H fi-brornopropionic acid chloride 5 D o C H3C Hz H 2, 4-dichloro-S-methylpyrimidine-5-carboxy 6 D o CH2-CHg- H 2, 4-dichloro-6carboxymethylamino-l, 3, 5-trizine- 3 Do. --0 Hz-C H2- H cyanuric chloride, then '-(B-hydroxypropyD-amine 11 D o CH OHZ H rr-bromoacrylic acid-chloride 5 D0, 0 Hg-O H H 2,4-dib romo'5-bromomethyl-6-methylpyrimidine 1 D o -C Hz-C Hz- H 2,4dichloro-5-chloromethylriyrimidine 1 D 0 C Hr-C H2- H a,/S-dichloroacrylic acid chloride 5 Do -C HzC 112- H 6, B-dichloroacrylic acid chloride 5 Do C Hz-C H2- H 'y-chlorocrotouic acid chloride 5 D o --CHzCHz- H 'y-br0n1ocrotonic acid chloride- 5 Do. --0 H C H H vinylsulionic acid chloride 5 D0. 0 Bi -C Hz- H 2,4-dibromopyrimidine-5-tzarboxylic acid chloride 6 Do. 0 Hz-C Hg H 2,3-dibromoquinoxaline-G-carh oxylic acid bromide 6 D o 0 H Hz- H cyanuric bromide, then methylamine 2 D0 C H2C H2- H cyanuric chloride, then aminobenzene 2 Do -C Hz-C Hz- H cyanuric chloride, then 4-methyl-1-aminobenzen 2 D o. C Hr-C H2 H cyanuric chloride, then N-methyl-aminobenzene 2 Do. --0 HT-C H:- H cyanuric chloride, then N -fi-hydroxyethylaminobenzene 2 Do C Hz-C H- H 2, 4-dichloro-6-di- (fl-hydroxyethyl) amino-1,3, S-triazine 3 Do.

TABLE Substit- Example Radical A uent Z Reactive Component Procedure as Shade Number (I) (II) (III) in Example (IV) (V) 58 -G H2C H H B-ehloropropionic acid chloride V 5 Scarlet.

59 -CH2O H2 H cyanuric chloride, then 3methoxypropylamine. 2 Do. 60-- -G Hz-C H2- H 2,4-dichloro6- (2 ,4'-disulfopheny1amino)-1,3,5-tr1 3 D0. 61 *C H2C Hg H 2, 4-dich1oro-6-( dcarb oxyethylamin0)-1, 3, S-trizine 3 D o. 62- -C HzC Hz- H 2, 4-dichloro-fi-(4-snlfonaphthyl-1-amino)-1, 3, 5-tria 3 Do. 63 G Hz-C 112- H 2, 4-dichloro-6-(6'-sulfonaphthyl-2'-amino) 1, 3. 5-triazine 3 Do. CH2C H2' H 2, 4-dichlor0-6-(N-ethyl-N-B-carbcxyethylarnino)1 3 5- 3 Do. H cyannn'c chloride, then ethylamine 2 Do. H cyanuric chlon'de, then fl-ethyoxyethylamin 2 Do. H cyanuric chloride, then 4-carboxy-l-aminobenzene- 2 Do. H cyannric chloride, then 3-methox-ybutylamine 2 Do. H fl-snlfato-ethylsnlfonic acid chloride 5 D H 2,4-dichlor0fi-(2'-carb0xy-5-sulfophenylamino)-l,3, 3 Do. H 2,4-dichloro-6-(2,4-dicarboxyphenylamino)-l,3,5-triazine 3 Do. H cyanun'c chloride, then 2-methoxyethylamine 2 Do. H cyanuric chloride, then 3-hydroxypropylamine 2 Do. H 2,4-dichloro-6-phenoxy-l,8, E triazine 3 D0. H 2,4-dichloro-6-methoXy-l,3,5-triazine 3 Do. H 2,4-dichloro-6-ethoxy-1,3,5-triazine 3 Do. H cyanuric chloride, then N-methyl-N by y y 2 Do. H 2, i-dibromofi-(4-suliophenylamino)-l, 3, strizaine 3 Do. H 2, 4 -dichloro-6-(2, 5-dicarboxyphenylamino)-1, 3, S-triazine- 3 Do. H 2, 4-dich1oro-6-(N-methyl-N-B-sulfoethylamino)4,3, fi-triazin 8 Do. H 2, -dichloro-S-(3,B'-disnlfonaphthyl-1'-amino)-1,3, 5-triazine 3 Do. H 2, 4-dichloro-6-(4" 8-disnlfonaphthyLW-amino)-1, 3, 5-triazine 3 Do.

11 2, A-dichloro-G-(Z, 5-disulf0phenylamino)-1, 3, fi-triazine 3 Do.

H 2,4-dichloro-6-(2carboxy-4-snlfophenylamino)-1,3,&triazine 3 Do. H 2,4-dichloro-6-(N-methyi-N-carboxymethyalmino)-1,3,5-triazine. 3 Do. H 2,4-diehloro-6- (4',6-disu1fonaphthyl-1-amino)-1,3,5-triazine 3 Do -C Hz-C Hz- H a,B-dichloropropionic acid chloride 5 Do.

Formulae of representative dyes of the foregoing examples are as follows:

Examples 1 and 4 35 Example 2 Example 3 Example 7 N HOaS -NHO cg E01 01 Example 8 Example 24 Example 27 0 HOaSOCzH|O N=N 01 N HOaS NH-OHr- 431 -N Ha N Having thus disclosed the invention what I claim is: X is 02s C 1. A reactive dye of the formula wherein A is a member selected from the group con- 7 Example sisting of 0H HOSSCZH4 OC N=N I T N038 NH- H L C].

Example 10 -CH2CH2, CH2CH2-CHz-, CH-CHz-, -CH2CE 0H CHa CH3 N NH /N 01 and HOaS-O-C2H4- I I 0 H CH2 HOaS OH Y X is a reactive radical selected from the group consisting of monohalo (lower) alkanoyl, dihalo (lower) a1- kanoyl (lower) alkenoyl, mono-halo (lower) alkenoyl, 0H dihalo (lower) alkenoyl, mono-halo (lower) a1kylsul fonyl (lower) alkenylsulfonyl, sulfato (lower) alkyl- NH ILNHB sulfonyl, sulfato (lower) alkanoyl,

Example 11 N03s 5 2,4-dihalopyrimiclyl-S-carbonyl,

I 2,4-dihalo-6-methyl-pyrimidyl-5-carbonyl, Cl 2,4-dihalo-6-halomethyl-pyrimidyl-S-carbonyl, Example 22 2,4-dihalo-6-dihalomethyl-pyrimidyl-S-carbonyl, 01 OH 2,3-dihaloquinoxalyl-6-carbonyl-, N\ 2,3-dihaloquinoxaly1-6-sulfonyl, HOaS-O-CzH4-O -N= 2,3-dihal0quinoxaly1-6-aminocarbonyl;

L 4,6-dihalo-1,3,5-triazinyl-2-,

H0 is 01 4-halo-6- (lower) alkoxy-l 3 ,5 -triazinyl-2,

4-halo-6-phenoxy-l,3,5-triaziny1-2-, 1 4hal0-6-amino-1,3,5-triazinyl-2,

0H rams-o-cnn-o-Orwzv N 1103s NH-f IN 1 6 4-halo-6-carboxyphenylamino-1,3,5-triazinyl-2, 4-halo-6-su1fophenyl-amino-l 3 ,5 -tri azinyl-Z, 4-halo-6-dicarboxyphenylamino-1,3,5-triazinyl-2, 4-halo-6-carboxysulfophenylaminod,3,5-tfiaziny1-2,

4-halo-6-disulfophenylamino-1,3,5-tria;iny1-2;

4-hal0-6-sulfonaphthylamino-1,3,5-triaZinyl-2, 4-ha1o-6-disulfonaphthylamino-l,3,5-triazinyl-2,

' 2,4-dihaIO-G-methylpyrimidyl-S-methy1ene,

2,4-dihalopyrimidyl-5 -methy1ene, dihalo-pyrimidyl, trihalopyrimidyl, S-lower alkyl-dihalopyrimidyl,

S-lower alkoxy-carbonyl-dihalopyrimidvl,

1 5-carboxy-dihalopyrimidyl,

S-halomethyl-dihalopyrimidyl, and 5-carboxy-methyl-dihalopyrimidyl, halogen being chlorine or bromine,

and Z is a member selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl and -COOH.

2. The reactive dye according to claim 1 of the formula 3. The reactive dye according to claim 1 of the formula SOaH 4. The reactive dye according to claim 1 of the formula 5. The reactive dye according to claim 1 of the formula 6. The reactive dye according to claim 1 of the formula References Cited FOREIGN PATENTS 1,252,324 12/1960 France.

CHARLES B. PARKER, Primary Examiner D. M. PAPUGA, Assistant Examiner U.S. Cl. X.R.

PRIN I 2H; IHIM LIN Patent No. 2 5 Dated August 4, 1970 Philippe Grandjean Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In column 1, line 53, "-nyrimidin" should he nyrim'idine.

In column 2, line 8, "5,-triazine" should be --5 triaz'ine; line 15, "HO-CH CH- -CH should be --1:o-cz -cu -c1z line l6,"'H OCH -C1I" should be -IlO-C7-I -C1l,-;

CH3 CH3 line 42, "-89 should be --SO i1-. In column 4, line 7, "triazinyl-Z" should be --triazinyl2,-; line 52, "preferably," should be --preferabl v-; line 73,

preferably" should be -pr-eferablebe -medium-.

In column 5, line 27, "medium" should In column 6, line 65, "apprecially" should be -appreciahl In column 7, line 60,

"tricholoropyrimidvlamino" should be trichlorooyrimidylaminoline 74 line 68, "orthoposition" should be ortho-position-.

"Scarlets should he -scarlet-. In column 8, line 22, "chloropropylamino" should he --chlor opropionylamino-; line 65, "amino 5-" should be -amino-5- In columns 9/10, in the table, Examnle No. 16, "pyridine" should be --pvrimidine--; Example 1-10. 40, "trizine" should be triz1zine. In column 12, in the table No. 63, "nmino)l,"

should be -ethox Example No. 61, "-trizine" should be -triazine--; Example should be amir:o)-l,-; Example. 170. (16, "ethyoxyethylamine" ethy1amine--; Example T310. (-8, "methoxvhutylamine" should be --methoxy-butvlamine- Examole 210. 78, "trizaine" sh o uld he -t.riaEine--; Example No. 84, (2' carhoxy" should be (2'-carhox v--.

In column 13, in the structure of Example 9,

USCOMNhDC GOING-P60 I u sv GOVIINNINY PIINHNG ornc: nu O-diI-lll FORM PO-1U5O (10-69) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. D t d August 4,

Philippe Grandjean PAGE 2 Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

C1" should be V' N "N0 3 should be --IIO S- V C1 in the structures of Exam le 10, and 11 respectively,

Should be in the structure of Example 11, "Q"

aim-K should be G "NO 8'' should he I- O S--. In column 14, in the structure 3 3 of Example 24, m should be u 1 II Cl in the structure of Exam le 27, O should he OII In column 13, in the structure of Example 22, should be In column 14,

I FORM o-1050 (10-69) USCOMM-DC 60376-P69 i ".5, GOVIIIMINT 'RINTING OFFICE: IIII O-J'I-S UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,523,115- Dated August 1970 Philippe Grandjean A E '3 Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

line 60 "kanovl should he --kanovl,-; line 62, "fonyl" should "sulfate" should he --sulfatoline 74, "triazinyl2," should be --triazinyl-2,--. In column 16, in the structure of claim 5, a C1 II should be N (SEAL) Attest:

EDWARD M. FLETCHER,JR. Attesting Officer ROBERT GOTTSCHALK Commissioner of Patents FORM PO-105O (10-69] USCOMM-DC 608764 09 ".5. GOVERNMENT PIINYING OFFICE ll. 0-Si-SS4 be --fony1,-; 

